Method for producing bleach activator granules

ABSTRACT

The present invention relates to methods for producing bleach-activator-containing granules from a water-containing bleach activator preparation form by granulation and simultaneous drying in a fluidized-bed and subsequent consolidation of the primary granules by treatment with an aqueous polymer and/or phosphonate solution, in a fluidized bed.

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application is a continuation of PCT/EP02/13126 filedNovember22, 2002, which claims the benefit of DE 101 59 386.4 filed Dec.4, 2001, the complete disclosures of which are hereby incorporated byreference in their entirety.

FIELD OF THE INVENTION

[0002] The invention relates to a method for producingbleach-activator-containing granules from a water-containing bleachactivator preparation form by granulation and simultaneous drying in afluidized-bed and subsequent consolidation of the primary granules bytreatment with an aqueous polymer and/or phosphonate solution, likewisein a fluidized bed.

BACKGROUND OF THE INVENTION

[0003] As well as comprising ingredients which are indispensable for thewashing process, such as surfactants and builder materials, detergentsand cleaners usually comprise further constituents which can besummarized under the term washing auxiliaries and include various groupsof active ingredients, such as foam regulators, graying inhibitors,bleaches and color transfer inhibitors. Such auxiliaries also includesubstances which aid the surfactant performance as a result of oxidativedegradation of soilings located on the textile or those in the liquor.Analogous statements also apply to cleaners for hard surfaces. Forexample, inorganic peroxygen compounds, in particular hydrogen peroxideand solid peroxygen compounds which dissolve in water to liberatehydrogen peroxide, such as sodium perborate and sodium carbonateperhydrate, have been used for a long time as oxidizing agents fordisinfection and bleaching purposes. The oxidative effect of thesesubstances greatly depends on the temperature in dilute solutions; thus,for example, with H₂O₂ or sodium perborate in alkaline bleachingliquors, sufficiently rapid bleaching of soiled textiles usually onlytakes place at temperatures above about 60° C. At lower temperatures itis possible to improve the oxidative effect of the inorganic peroxygencompounds by adding so-called bleach activators, for which numerousproposals, primarily from the classes of substance of N- or O-acylcompounds, for example polyacylated alkylenediamines, in particulartetraacetylethylenediamine, acylated glycolurils, in particulartetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles,hydrotriazines, urazoles, diketopiperazines, sulftirylamides andcyanurates, and also carboxylic anhydrides, in particular phthalicanhydride, carboxylic esters, in particular sodiumnonanoyloxybenzenesulfonate, sodium isononanoyloxybenzenesulfonate andacylated sugar derivatives, such as pentaacetylglucose, have becomeknown in the literature. The addition of these substances can increasethe bleaching action of aqueous peroxide liquors such that even attemperatures below 60° C. essentially the same effects arise as with theperoxide liquor on its own at 95° C.

[0004] European patent application EP 0 464 880 disclosesbleach-boosting cationic nitriles of the general formula R′R″ R′″N⁺-CR₁R₂—CN X⁻, in which R₁ and R₂ are hydrogen or a substituent with atleast one carbon atom, R′ is a (C₁-C₂₄)-alkyl, -alkenyl or -alkyl ethergroup or —CR₁R₂—CN, and R″ and R′″ are each case (C₁-C₂₄)-alkyl orhydroxyalkyl group, and the counteranion X⁻ is an organic sulfonate, anorganic sulfate or a carboxylate.

[0005] International patent application WO 98/23719 discloses thatcompounds of the general formula R¹R²R³N⁺CH₂CN X⁻, in which R¹, R² andR³, are independently alkyl, alkenyl or aryl group having 1 to 18 carbonatoms, where the groups R² and R³ may also be part of a heterocycleincluding the N atom and optionally containing further heteroatoms, andX⁻ is a charge-balancing anion, can be used as activators for, inparticular, inorganic peroxygen compounds in aqueous dishwashingsolutions. This provides an improvement of the oxidative and bleachingeffect in particular of inorganic peroxygen compounds at lowtemperatures below 80° C., in particular in the temperature range fromabout 15° C. to 55° C. At least some of these cationic nitriles,however, are produced in the course of their production in liquid form,for example as in particular aqueous solution, and can only be convertedfrom these into the pure solid with considerable losses, meaning thattheir use in solid, for example particulate, compositions presentsdifficulties. In addition, cationic nitriles, particularly incombination with further ingredients of detergents and cleaners, arenormally not very storage-stable and in particular sensitive tomoisture.

[0006] International patent application WO 00/50556 discloses theproduction of solid preparations which comprise cationic nitrile andsolid carrier material by a vacuum steam-drying method in a mixer.Although this method produces bleach activator granules, attempts arenevertheless made to develop an alternative production method which isas simple as possible.

SUMMARY OF THE INVENTION

[0007] An object of the invention was therefore to provide a productionmethod with which aqueous preparations comprising a cationic nitrile canbe converted into particulate preparations such that thebleach-activating active substance of the cationic nitrile can beincorporated into solid detergents and cleaners as far as possiblewithout loss. It has now been found that the production of suchpreparations is possible by a fluidized-bed granulation method. In thismethod, drying and granulation can be carried out in a simple manner inone device, with the production of granules with a particularly highcontent of cationic nitrile being readily possible

[0008] These and other aspects of the invention will become moreapparent from the detailed description and claims.

DETAILED DESCRIPTION OF THE INVENTION

[0009] In one embodiment, the present invention provides methods forproducing a particulate preparation comprising a compound according toformula (I),

[0010] wherein:

[0011] R¹ is —H, —CH₃, optionally substituted (C₂-C₂₄)-alkyl radical,optionally substituted (C₂-C₂₄)-alkenyl radical, optionally substitutedalkyl radical containing a (C₁-C₂₄)-alkyl group, or optionallysubstituted alkenylaryl radical containing a (C₁-C₂₄)-alkyl group;

[0012] R² and R³ are independently —CH₂—CN, —CH₃, —CH₂—CH₃,—CH₂—CH₂—CH₃, —CH(CH₃)—CH₃, —CH₂—OH, —CH₂—CH₂—OH, —CH(OH)—CH₃,—CH₂—CH₂—CH₂—OH, —CH₂—CH(OH)—CH₃, —CH(OH)—CH₂—CH₃, or —(CH₂CH₂—O)_(n)H;

[0013] R⁴ and R⁵ are independently —H, —CH₃, optionally substituted(C₂-C₂₄)-alkyl radical, optionally substituted (C₂-C₂₄)-alkenyl radical,optionally substituted alkyl radical containing a (C₁-C₂₄)-alkyl group,optionally substituted alkenylaryl radical containing a (C₁-C₂₄)-alkylgroup, —CH₂—CN, —CH₂—CH₃, —CH₂—CH₂—CH₃, —CH(CH₃)—CH₃, —CH₂—OH,—CH₂—CH₂—OH, —CH(OH)—CH₃, —CH₂—CH₂—CH₂—OH, —CH₂—CH(OH)—CH₃,—CH(OH)—CH₂—CH₃, or —(CH₂CH₂—O)_(n)H;

[0014] n is an integer of 1, 2, 3, 4, 5 or 6;

[0015] X⁽⁻⁾ is a charge-balancing anion,

[0016] wherein said particulate is produced by the steps:

[0017] a) preparation of an aqueous solution comprising cationic nitrileof formula (I) and optionally alkali metal cumenesulfonate, inparticular sodium cumenesulfonate,

[0018] b) optional adjustment of the solution to an acidic pH, inparticular by adding sulfuric acid and/or citric acid,

[0019] c) atomization and drying of the solution in a fluidized-bedapparatus,

[0020] d) optional powdering of the resulting primary granules usingsilica, zeolite and/or Na cumenesulfonate in the fluidized bed,

[0021] e) consolidation of the optionally powdered primary granules bysubsequent spraying with an aqueous consolidation solution, saidsolution comprising polymeric polycarboxylate and/or alkali metalphosphonate as consolidation active ingredient, with simultaneous dryingin the same or optionally a downstream second fluidized-bed apparatus,

[0022] f) discharge of the granules from the fluidized-bed apparatus andoptional separation of the granules into acceptable granules andcoarse/fine granules, in particular by sieving,

[0023] g) optional return of fine granules and/or ground coarse granulesinto the fluidized bed in step c), and

[0024] h) optional return of fine granules and/or ground coarse granulesinto the powdering step d).

[0025] In another embodiment, the present invention provides methodsproducing a particulate preparation comprising:

[0026] providing an aqueous solution comprising a cationic nitrile offormula (I):

[0027] wherein:

[0028] R¹ is —H, —CH₃, optionally substituted (C₂-C₂₄)-alkyl radical,optionally substituted (C₂-C₂₄)-alkenyl radical, optionally substitutedalkyl radical containing a (C₁-C₂₄)-alkyl group, or optionallysubstituted alkenylaryl radical containing a (C₁-C₂₄)-alkyl group;

[0029] R² and R³ are independently —CH₂—CN, —CH₃, —CH₂—CH₃,—CH₂—CH₂—CH₃, —CH(CH₃)—CH₃, —CH₂—OH, —CH₂—CH₂—OH, —CH(OH)—CH₃,—CH₂—CH₂—CH₂—OH, —CH₂—CH(OH)—CH₃, —CH(OH)—CH₂—CH₃, or —(CH₂CH₂—O)_(n)H,wherein n is an integer of 1, 2, 3, 4, 5 or 6;

[0030] R₄ and R₅ are independently R1 or R2; and X⁽⁻⁾ is acharge-balancing anion;

[0031] atomizing and drying the solution in a fluidized-bed apparatus toform primary granules;

[0032] consolidating the granules by subsequent spraying with an aqueousconsolidation solution with simultaneous drying; and

[0033] discharging the granules from the fluidized-bed apparatus.

[0034] The terms “optionally substituted (C₂-C₂₄)-alkyl” or “optionallysubstituted (C₂-C₂₄)— alkenyl radical”, as used herein, includes thosealkyl or alkenyl radicals that are optionally substituted with at leastone substituent selected from the group comprising —Cl, —Br, —OH, —NH2,and —CN.

[0035] The term “optionally substituted alkenylaryl radical”, as usedherein, includes those alkenylaryl radicals that are optionallysubstituted with a (C₁-C₂₄)-alkyl group and which further contain atleast one substitutent on the aromatic ring.

[0036] The resulting bleach activator granules or the acceptable granulefraction thereof preferably has/have average particle diameters in therange from 0.2 mm to 2.5 mm, in particular in the range from 0.4 mm to2.0 mm. Its bulk density is preferably in the range from 300 g/l to 1000g/l, in particular in the range from 400 g/l to 800 g/l. The proportionof compound according to formula (I) is preferably in the range from 10%by weight to 90% by weight, in particular from 15% by weight to 50% byweight. It is preferably used for producing particulate detergents orcleaners.

[0037] The method according to the invention preferably starts from anaqueous solution of the compound according to formula (I), as isproduced in its preparation. In this, the concentration of compoundaccording to formula (I) is preferably 10% by weight to 90% by weight,in particular from 15% by weight to 50% by weight. It is optionallymixed with alkali metal cumenesulfonate, which can be used in the formof a solid or in the form of an aqueous solution and is preferably usedin quantitative ratios (compound according to formula (I) to alkalimetal cumenesulfonate) of from 10:1 to 1:5, in particular from 2:1 to1:2, the pH is adjusted to an acidic value, where one is not alreadypresent, by adding system-compatible acid, for example sulfuric acidand/or citric acid, and the solution is sprayed in a fluidized-bedapparatus above an inflow base provided with openings for the fluidizinggas, in particular fluidizing air, as a result of which water is removedfrom it and granules form. Fluidized-bed devices which can be used in amethod according to the invention are known, for example, from Europeanpatent specification EP 0 603 207 B1 or German patent application DE 19750 424. In order to further reduce the possibility of the granulesfalling through the openings in the inflow base, which would result inthem coming into contact with surfaces at a relatively high temperature,the openings can be covered by a grid, in particular with mesh widthsless than 600 μm. Here, the grid may be arranged within or above theopenings. However, the grid is preferably directly below the openings inthe inflow base, as is known in principle from German patent applicationDE 197 50 424. In one practical variant, a metal gauze with anappropriate mesh width can be sintered, or attached in some other way,to the underside of an inflow base known per se. The metal gauzepreferably consists of the same material as the inflow base, inparticular of stainless steel. The fine-mesh grid prevents particlesfrom falling through, particularly when the granulation plant is shutdown unexpectedly, but also especially in the case of particularly heavyparticles with bulk densities around 1000 g/l also during operation. Themesh width of said grid is preferably between 200 and 400 μm. Inaddition, it is advantageous if the inflow base used has a pressure lossof at most 10 mbar and in particular at most 6 mbar.

[0038] In order to improve the pourability of the resulting primarygranules, they may then be powdered in the granulation step with finelydivided material chosen from silica, zeolite and/or Na cumenesulfonate.

[0039] The optionally powdered primary granules are then optionallytransferred to a second fluidized-bed apparatus (“consolidationapparatus”), which may be of identical construction to the fluidized-bedapparatus used above, and are sprayed with an aqueous consolidationsolution. Suitable consolidation active ingredients are polymericpolycarboxylates, in particular polymerization products of acrylic acid,methacrylic acid or maleic acid, or copolymers of at least two of these,which are used in completely or at least partially neutralized form, inparticular in the form of the alkali metal salts. Alkali metalphosphonate can be used as an alternative to or in addition to thepolymeric polycarboxylate. In said alkali metal salts, sodium is thealkali metal preferred in each case. The consolidation liquid ispreferably adjusted to the lowest possible viscosity for good dropdistribution upon atomization in the consolidation apparatus withsimultaneous drying.

[0040] Finally, the granules are discharged from the fluidized bed in amanner known in principle and optionally classified according toparticle size, where undesirably small particles (fine granules) andundesirably large particles (coarse granules) can be returned to theprocess following a grinding step. If desired, they can be returned tothe granulation step or to the powdering step or to both steps. In oneparticular variant of the method according to the invention, theclassified acceptable granules can again be introduced into afluidized-bed apparatus, and consolidation solution be sprayed onto themin order, if necessary, to further improve the product properties of thegranules.

[0041] Compounds according to formula I can be produced by knownprocesses or in accordance with these, as have been published, forexample, in said patent literature or by Abraham in Progr. Phys. Org.Chem. 11 (1974), p. 1 ff, or by Arnett in J. Am. Chem. Soc. 102 (1980),p. 5892 ff.

[0042] Preference is given to the use of compounds according to formulaI in which R¹, R² and R³ are identical. Of these, preference is given tothose compounds in which said radicals are methyl groups. On the otherhand, preference is also given to those compounds in which at least 1 or2 of said radicals are methyl groups and the other radical, or the otherradicals, have two or more carbon atoms.

[0043] The anions X⁽⁻⁾ include, in particular, the halides, such aschloride, fluoride, iodide and bromide, nitrate, hydroxide, phosphate,hydrogenphosphate, dihydrogenphosphate, pyrophosphate, metaphosphate,hexafluorophosphate, carbonate, hydrogencarbonate, sulfate,hydrogensulfate, C₁₋₂₀-alkyl sulfate, C₁₋₂₀-alkylsulfonate, optionallyC₁₋₁₈-alkyl-substituted aryl-sulfonate, chlorate, perchlorate and/or theanions of C₁₋₂₄-carboxylic acids, such as formate, acetate, laurate,benzoate or citrate, alone or in any mixtures. Preference is given tocompounds according to formula I in which X⁽⁻⁾ is chloride, sulfate,hydrogensulfate, ethosulfate, C_(12/18)-, C_(12/16)-or C_(13/15)-alkylsulfate, lauryl sulfate, dodecylbenzenesulfonate, toluenesulfonate,cumenesulfonate, xylenesulfonate or methosulfate or mixtures thereof.Toluenesulfonate, or cumenesulfonate, is understood here as meaning theanion of the ortho-, meta- or para-isomers of methylbenzenesulfonicacid, or isopropylbenzenesulfonic acid, respectively, and any mixturesthereof. para-Isopropylbenzenesulfonic acid is particularly preferred.

[0044] Granules produced by the method according to the invention arestorage-stable, readily pourable and of adequate granule stability inorder to permit them to be mixed with other particulate constituents ofdetergents or cleaners in a customary manner. The bleach-activatingeffect of the compound according to formula (I) is not significantlyimpaired by the method. Granules prepared by the method according to theinvention are used in particular in particulate detergents and cleaners,preferably in amounts such that these compositions have contents of from0.1% by weight to 10% by weight, in particular from 0.2% by weight to 7%by weight, of bleach activator according to formula (I).

EXAMPLES Example 1

[0045] Granules were prepared in a fluidized-bed apparatus (Glatt® AGT400 with a diameter of 40 cm) with 400 m³/h of incoming air stream, anincoming air temperature of 95° C. and an outgoing air temperature of55° C. from a homogeneous aqueous solution of trimethylammoniumacetonitrile methosulfate and sodium cumenesulfonate (mass ratio 1:1,dry-substance fraction 30%) at a solution throughput of 3 kg/h over thecourse of 5 h; the granules were still very tacky. The tackiness wasovercome by granulating again with a 20% strength aqueous solution ofpolymeric polycarboxylate (Sokalan® CP45, manufacturer BASF) under thesame conditions with regard to incoming air stream, incoming airtemperature and outgoing air temperature. The polymer fraction in thegranules obtained in this way was 5% by weight. The size of the granuleswas in the range from 0.4 mm to 2.0 mm, the bulk density was 700 g/l.The granules were then sieved and the proportion with granule sizes ofbetween 0.8 and 1.6 mm was mixed with the other detergent components ofa detergent formulation. The finished detergent could be used withoutclumping.

Example 2

[0046] In a fluidized-bed apparatus with a diameter of 1.8 m (Glatt® AGT1800), primary granules were prepared from a 40% strength aqueoussolution of the cationic nitrile used in example 1, with powdering withNa cumenesulfonate powder. The amount of incoming air was 21 000 m³/h,the incoming air temperature was 145° C. The outgoing air temperaturewas adjusted to 65° C. by evaporating the water in this solution. After1 h, the batch-operated fluidized bed was so full that the granulationwas stopped. The consolidation was carried out using the 20% strengthpolymer solution used in example 1 at an incoming air temperature of110° C. The polymer content in the finished granules was 10% by weight.The resulting granules were sieved off between 0.8 and 1.6 mm. The bulkdensity was 730 g/l.

[0047] The finished granules were processed with customary particulatedetergent components to give a particulate detergent.

Example 3

[0048] In a fluidized-bed apparatus with a diameter of 1.8 m (Glatt® AGT1800), primary granules were prepared from a 40% strength aqueoussolution of the cationic nitrile used in Example 1, with powdering withsilica powder (Thixosil® 38A). The amount of incoming air was 20 000m³/h, the incoming air temperature was 140° C. The outgoing airtemperature was adjusted to 65° C. by evaporating the water in thissolution. After 1 h, the batch-operated fluidized bed was so full thatthe granulation was stopped. The consolidation was carried out using the20% strength polymer solution used in example 1 at an incoming airtemperature of 110° C. The polymer content in the finished granules was7% by weight. The resulting granules were sieved off between 0.8 and 1.6mm. The bulk density was 710 g/l.

Example 4

[0049] The granules obtained according to example 2 were introducedagain into the fluidized-bed apparatus, where they were sprayed from theside with the 20% strength polymer solution already used above at anincoming air temperature of 130° C. and an outgoing air temperature of65° C. to give a 20% by weight coating. Similarly, the granules obtainedaccording to example 3 were again introduced into the fluidized-bedapparatus where they were sprayed from the side with the 20% strengthpolymer solution at an incoming air temperature of 130° C. and anoutgoing air temperature of 65° C. to give a 10% by weight coating.

[0050] The disclosures of each patent, patent application, andpublication cited or described in this document are hereby incorporatedherein by reference, in their entireties.

[0051] Various modifications of the invention, in addition to thosedescribed herein, will be apparent to those skilled in the art from theforegoing description. Such modifications are also intended to fallwithin the scope of the appended claims.

What is claimed:
 1. A method for producing a particulate preparationcomprising a compound according to formula (I):

wherein: R¹ is —H, —CH₃, optionally substituted (C₂-C₂₄)-alkyl radical,optionally substituted (C₂-C₂₄)-alkenyl radical, optionally substitutedalkyl radical containing a (C₁-C₂₄)alkyl group, or optionallysubstituted alkenylaryl radical containing a (C₁-C₂₄)-alkyl group; R²and R³ are independently —CH₂—CN, —CH₃, —CH₂—CH₃, —CH₂—CH₂—CH₃,—CH(CH₃)—CH₃, —CH₂—OH, —CH₂—CH₂—OH, —CH(OH)—CH₃, —CH₂—CH₂—CH₂—OH,—CH₂—CH(OH)—CH₃, —CH(OH)—CH₂—CH₃, or —(CH₂CH₂—O)_(n)H; R₄ and R₅ areindependently —H, —CH₃, optionally substituted (C₂-C₂₄)-alkyl radical,optionally substituted (C₂-C₂₄)-alkenyl radical, optionally substitutedalkyl radical containing a (C₁-C₂₄)-alkyl group, optionally substitutedalkenylaryl radical containing a (C₁-C₂₄)-alkyl group, —CH₂—CN,—CH₂—CH₃, —CH₂—CH₂—CH₃, —CH(CH₃)—CH₃, —CH₂—OH, —CH₂—CH₂—OH, —CH(OH)—CH₃,—CH₂—CH₂—CH₂—OH, —CH₂—CH(OH)—CH₃, —CH(OH)—CH₂—CH₃, or —(CH₂CH₂—O)_(n)H;n is an integer of 1, 2, 3, 4, 5 or 6; X⁽⁻⁾ is a charge-balancing anion;said particulate produced by the steps: a) preparation of an aqueoussolution comprising cationic nitrile of formula (I) and optionallyalkali metal cumenesulfonate; b) optional adjustment of the solution toan acidic pH; c) atomization and drying of the solution in afluidized-bed apparatus; d) optional powdering of the resulting primarygranules in the fluidized bed; e) consolidation of the optionallypowdered primary granules by subsequent spraying with an aqueousconsolidation solution, with simultaneous drying in the same oroptionally a downstream second fluidized-bed apparatus; f) discharge ofthe granules from the fluidized-bed apparatus and optional separation ofthe granules into acceptable granules and coarse/fine granules; g)optional return of the fine granules and/or the ground coarse granulesinto the fluidized bed in step c); and h) optional return of the finegranules and/or the ground coarse granules into the powdering step ofstep d).
 2. The method of claim 1, wherein the concentration of saidcompound of formula (I) is from about 10% by weight of said aqueoussolution to about 90% by weight of said aqueous solution.
 3. The methodof claim 1, wherein the concentration of said compound of formula (I) isfrom about 15% by weight of said aqueous solution to about 50% by weightof said aqueous solution.
 4. The method of claim 1, wherein saidcompound of formula (I) and said alkali metal cumenesulfonate arepresent in a ratio of from about 10:1 compound of formula (I):alkalimetal cumenesulfonate, to about 1:5 compound of formula (I):alkali metalcumenesulfonate.
 5. The method of claim 1, wherein said compound offormula (I) and said alkali metal cumenesulfonate are present in a ratioof from about 2:1 compound of formula (I):alkali metal cumenesulfonate,to about 1:2 compound of formula (I):alkali metal cumenesulfonate. 6.The method of claim 1, wherein said alkali metal cumenesulfonate issodium cumenesulfonate.
 7. The method of claim 1, wherein said acidic pHis adjusted by the addition of sulfuric acid, citric acid, orcombinations thereof.
 8. The method of claim 1, wherein said primarygranules are powdered with silica, zeolite, Na cemenesulfonate, orcombinations thereof.
 9. The method of claim 1, wherein said aqueousconsolidation solution comprises polymeric polycarboxylate, alkali metalphosphonate, or combinations thereof as the consolidation activeingredient.
 10. The method of claim 1, wherein said polymericpolycarboxylate is polymerization products of acrylic acid, methacrylicacid, maleic acid, copolymers of at least two the polymerizationproducts, in at least partially neutralized form.
 11. The method ofclaim 1, wherein said copolymers are in the form of alkali metal salts.12. The method of claim 1, wherein said alkali metal salt is sodium. 13.The method of claim 1, wherein said separation of the granules is bysieving.
 14. The method of claim 1, wherein said R¹, R² and R³ are thesame.
 15. The method of claim 1, wherein said R¹, R², and R³ are —CH₃.16. The method of claim 1, wherein 1 or 2 of said R¹, R² and R³ radicalsare —CH₃ and at least one of said R¹, R² and R³ radicals contains 2 ormore carbon atoms.
 17. The method of claim 1, wherein said X⁽⁻⁾ ishalide, nitrate, hydroxide, phosphate, hydrogen phosphate, dihydrogenphosphate, pyrophosphate, metaphosphate, hexafluorophosphate, carbonate,hydrogencarbonate, sulfate, hydrogensulfate, (C₁-C₂₀)-alkyl sulfate,(C₁-C₂₀)-alkylsulfonate, optionally substituted (C₁-C₁₈)-alkylarylsulfonate, chlorate, perchlorate, an anion of (C₁-C₂₄)-carboxylicacid, or combinations thereof.
 18. The method of claim 1, wherein saidX⁽⁻⁾ is chloride, sulfate, hydrogen sulfate, methosulfate, ethosulfate,(C₁₂-C₁₈)-alkyl sulfate, (C₁₂-C₁₆)-alkyl sulfate, (C₁₃-C₁₅)-alkylsulfate, lauryl sulfate, dodecylbenzenesulfonate, toluenesulfonate,cumenesulfonate, xylenesulfonate, para-isopropylbenzenesulfonic acid, orcombinations thereof.
 19. The method of claim 1, wherein saidparticulate preparation has an average particle diameter in a range offrom about 0.2 mm to about 2.5 mm.
 20. The method of claim 1, whereinparticulate preparation has an average particle diameter in a range offrom about 0.4 mm to about 2.0 mm.
 21. The method of claim 1, whereinthe bulk density of the particulate preparation is in a range of fromabout 300 g/l to 1000 g/l.
 22. The method of claim 1, wherein the bulkdensity of the particulate preparation in a range of from about 400 g/lto about 800 g/l.
 23. A particulate detergent or cleaner prepared by themethod of claim
 1. 24. The particulate detergent or cleaner of claim 23,wherein said granules are present in a range of from about 0.1% byweight to about 10% by weight.
 25. The particulate detergent or cleanerof claim 23, wherein said granules are present in a range of from about0.2% by weight to about 7% by weight.
 26. A method for producing aparticulate preparation comprising: providing an aqueous solutioncomprising a cationic nitrile of formula (I):

wherein: R¹ is —H, —CH₃, optionally substituted (C₂-C₂₄)-alkyl radical,optionally substituted (C₂-C₂₄)-alkenyl radical, optionally substitutedalkyl radical containing a (C₁-C₂₄)alkyl group, or optionallysubstituted alkenylaryl radical containing a (C₁-C₂₄)-alkyl group; R²and R³ are independently —CH₂—CN, —CH₃, —CH₂—CH₃, —CH₂—CH₂—CH₃,—CH(CH₃)—CH₃, —CH₂—OH, —CH₂—CH₂—OH, —CH(OH)—CH₃, —CH₂—CH₂—CH₂—OH,—CH₂—CH(OH)—CH₃, —CH(OH)—CH₂—CH₃, or —(CH₂CH₂—O)_(n)H, wherein n is aninteger of 1, 2, 3, 4, 5 or 6; R₄ and R₅ are independently R1 or R2; andX⁽⁻⁾ is a charge-balancing anion; atomizing and drying the solution in afluidized-bed apparatus to form primary granules; consolidating thegranules by subsequent spraying with an aqueous consolidation solutionwith simultaneous drying; and discharging the granules from thefluidized-bed apparatus.
 27. The method of claim 26 further comprisingproviding alkali metal cumenesulfonate in the aqueous solution.
 28. Themethod of claim 26 further comprising adjusting the aqueous solution toan acidic pH.
 29. The method of claim 26 further comprising powdering ofthe primary granules in the fluidized bed.
 30. The method of claim 26wherein consolidation takes place in a downstream second fluidized-bedapparatus.
 31. The method of claim 26 further comprising separating thegranules into acceptable granules and coarse/fine granules.
 32. Themethod of claim 26 further comprising returning the fine granules and/orthe ground coarse granules to the step of atomizing and drying.